"It's a shame. It's a sad situation," the pro card shark tells E! News of her fellow competitor on season two of The Celebrity Apprentice. "If what's being said is true, I certainly don't approve of it.
"Nobody wants to see that kind of devastation."
Duke made the remarks at her eponymous Texas Hold 'Em Poker Tournament to Benefit the 1736 Family Crisis Center on Saturday in Los Angeles. Other celebs in attendance included Shanna Moakler, Shannon Elizabeth, Sara Rue and castmembers of The Real Housewives of Beverly Hills.
While Duke notes Sandra Bullock wasn't present during filming of The Celebrity Apprentice in 2009, she says she never sensed that he had other women on the side.
"I think that everybody was surprised," says Duke, referring to her fellow castmates' reactions to James' headline-making marital woes. "I have to tell you that during the filming, I had nothing but good things to say about him. And I think everybody else felt the same way, too."
She and Jesse stayed in contact when filming ended, although they haven't spoken recently.
"I was in touch with him after the show, but I haven't been in touch with him since this happened," adds Duke. "I was in touch with him over the summer."
As host of the poker tournament, Duke was on hand to teach castmembers of The Real Housewives of Beverly Hills how to play the game. Although she's a fan of the Bravo franchise, Duke doesn't think she'd be a good fit on the show.
"I'd be such a silly housewife," she admits. "I don't go around with girlfriends, I just travel with a poker tour and then stay at home with the kids. I think I might be the only Real Housewife of Poker."
Love was in the cards for Sandra Bullock and Jesse James—or so it seemed. Take a look back at our Monster Love photo gallery!